Intercepting the Breslow intermediate via Claisen rearrangement: synthesis of complex tertiary alcohols without organometallic reagents.

A novel Claisen rearrangement in which the Breslow intermediate is engaged as a hydroxy-substituted N,S-ketene acetal to provide complex 3° alcohols without the use of organometallic reagents is reported. The reaction constitutes an unprecedented reactivity mode for the Breslow intermediate.